Middle distillate compositions with improved cold flow properties

ABSTRACT

The low temperature properties of a distillate petroleum fuel oil boiling in the range 120° C. to 500° C., and whose 20% and 90% distillation points differ by less than 100° C., and/or whose Final Boiling Point is in the range 340° C. to 370° C. are improved by the addition of a polymer or copolymer having at least 25 wt. % of n-alkyl groups of average number of carbon atoms from 12 to 14 with no more than 10 wt. % containing more than 14 carbon atoms.

Mineral oils containing paraffin wax have the characteristic of becomingless fluid as the temperature of the oil decreases. This loss offluidity is due to the crystallization of the wax into plate-likecrystals which eventually form a spongy mass entrapping the oil therein.

It has long been known that various additives act as wax crystalmodifiers when blended with waxy mineral oils. These compositions modifythe size and shape of wax crystals and reduce the adhesive forcesbetween the crystals and between the wax and the oil in such a manner asto permit the oil to remain fluid at a lower temperature.

Various pour point depressants have been described in the literature andseveral of these are in commercial use. For example, U.S. Pat. No.3,048,479 teaches the use of copolymers of ethylene and C₃ -C₅ vinylesters, e.g. vinyl acetate, as pour depressants for fuels, specificallyheating oils, diesel and jet fuels. Hydrocarbon polymeric pourdepressants based on ethylene and higher alpha-olefins, e.g. propylene,are also known. U.S. Pat. No. 3,961,916 teaches the use of a mixture ofcopolymers, one of which is a wax crystal nucleator and the other agrowth arrestor to control the size of the wax crystals.

U.K. Pat. No. 1263152 suggests that the size of the wax crystals may becontrolled by using a copolymer having a lower degree of side chainbranching.

It has also been proposed in for example U.K. Pat. No. 1469016 that thecopolymers of di-n-alkyl fumarates and vinyl acetate which havepreviously been used as pour depressants for lubricating oils may beused as co-additives with ethylene/vinyl acetate copolymers in thetreatment of distillate fuels with high final boiling points to improvetheir low temperature flow properties. According to U.K. Pat. No.1469016 these polymers may be C₆ to C₁₈ alkyl esters of unsaturated C₄to C₈ dicarboxylic acids particularly lauryl fumarate andlauryl-hexadecyl fumarate. Typically the materials used are mixed esterswith an average of about 12 carbon atoms (Polymer A). It is notable thatthe additives are shown not to be effective in the "conventional" fuelsof lower Final Boiling Point (Fuels III and IV).

U.S. Pat. No. 3,252,771 relates to the use of polymers of C₁₆ to C₁₈alpha-olefines obtained by polymerising olefin mixtures that predominatein normal C₁₆ to C₁₈ alpha-olefines with aluminium trichloride/alkyhalide catalysts as pour point and cloud point depressants in distillatefuels of the broad boiling, easy to treat types available in the UnitedStates in the early 1960's.

With the increasing diversity in distillate fuels, types of fuel haveemerged which cannot be treated by the existing additives or whichrequire an uneconomically high level of additive to achieve thenecessary reduction in their pour point and control of wax crystal sizefor low temperature filterability to allow them to be used commercially.One particular group of fuels that present such problems are those whichhave a relatively narrow, and/or low boiling range. Fuels are frequentlycharacterised by their Initial Boiling Point, Final Boiling Point andthe interim temperatures at which certain volume percentages of theinitial fuel have been distilled. Fuels whose 20% to 90% distillationpoint differ within the range of from 70° to 100° C. and/or whose 90%boiling temperature is from 10° to 25° C. of the final boiling pointand/or whose final boiling points are between 340° and 370° C. have beenfound particularly difficult to treat sometimes being virtuallyunaffected by additives or otherwise requiring very high levels ofadditive. All distillations referred to herein are according to ASTMD86.

With the increase in the cost of crude oil, it has also become importantfor a refiner to increase his production of distillate fuels and tooptimise his operations using what is known as sharp fractionation againresulting in distillate fuels that are difficult to treat withconventional additives or that require a treat level that isunacceptably high from the economic standpoint. Typical sharplyfractionated fuels have a 90% to final boiling point range of 10° to 25°C. usually with a 20 to 90% boiling range of less than 100° C.,generally 50° to 100° C. Both types of fuel have final boiling pointsabove 340° C. generally a final boiling point in the range 340° C. to370° C. especially 340° C. to 365° C.

The copolymers of ethylene and vinyl acetate which have found widespreaduse for improving the flow of the previously widely available distillatefuels have not been found to be effective in the treatment of the narrowboiling and/or sharply fractionated fuels described above. Furthermoreuse of mixtures as illustrated in U.K. Pat. No. 1469016 have not beenfound effective.

We have found however that polymers and copolymers containing veryspecific alkyl groups, such as specific di-n-alkyl fumarate/vinylacetate copolymers, are effective in both lowering the pour point of thedifficult to treat fuels described above and controlling the size of thewax crystals to allow filterability including those fuels of the lowerfinal boiling point in which the additives of U.K. Pat. No. 1469016 wereineffective.

Specifically we have found that the average number of carbon atoms inthe alkyl groups in the polymer or copolymer must be from 12 to 14 andthat no more than 10 wt.% of the alkyl groups should contain more than14 carbon atoms and preferably no more than 20 wt.% of the alkyl groupscontain fewer than 12 carbon atoms. These polymers are particularlyeffective when used in combination with other low temperature flowimprovers which on their own are ineffective in these types of fuels.

The present invention therefore provides the use for improving the flowproperties of a distillate petroleum fuel oil boiling in the range 120°C. to 500° C., whose 20% and 90% distillation points differ by less than100° C., and/or for improving the flow properties of a distillate fuelwhose 90% to final boiling point range is 10° to 25° C. and/or whoseFinal Boiling Point is in the range 340° C. to 370° C. of an additivecomprising a polymer containing at least 25 wt.% of n-alkyl groups, theaverage number of carbon atoms in the n-alkyl groups is from 12 to 14and no more than 10 wt.% of the alkyl groups contain more than 14 carbonatoms and preferably no more than 20 wt.% of the alkyl groups containfewer than 12 carbon atoms.

The additives are preferably used in an amount from 0.0001 to 0.5 wt.%,preferably 0.001 and 0.2 wt.% based on the weight of the distillatepetroleum fuel oil, and the present invention also includes such treateddistillate fuel.

The preferred polymer is a copolymer containing at least 25 preferablyat least 50 wt.% more preferably from 75 to 90 wt.% of a di-n alkylester of a dicarboxylic acid containing alkyl groups containing anaverage of 12 to 14 carbon atoms and 10 to 50 wt.% of anotherunsaturated ester such as a vinyl ester and/or an alkyl acrylate,methacrylate or alpha olefine. Equimolar copolymers of a di-n-alkylfumarate and vinyl acetate are particularly preferred.

The polymers or copolymers used in the present invention preferably havea number average molecular weight in the range of 1000 to 100,000,preferably 1,000 to 30,000 as measured, for example, by Vapor PressureOsmometry.

The carboxylic acid esters useful for preparing the preferred polymercan be represented by the general formula: ##STR1## where in R₁ and R₂are hydrogen or a C₁ to C₄ alkyl group, e.g., methyl, R₃ is the C₁₂ toC₁₄ average, straight chain alkyl group, and R₄ is COOR₃, hydrogen or aC₁ to C₄ alkyl group, preferably COOR₃. These may be prepared byesterifying the particular mono- or di-carboxylic acid with theappropriate alcohol or mixture of alcohols.

Other unsaturated esters, which can be copolymerized are the C₁₂ -C₁₄acrylates and methacrylates.

The dicarboxylic acid mono or di-ester monomers may be copolymerizedwith various amounts, e.g, 5 to 70 mole %, of other unsaturated estersor olefins. Such other esters include short chain alkyl esters havingthe formula: ##STR2## where R' is hydrogen or a C₁ to C₄ alkyl group, R"is --COOR"" or --OOCR"" where R"" is a C₁ to C₅ alkyl group branched orunbranched, and R"' is R" or hydrogen. Examples of these short chainesters are methacrylates, acrylates, the vinyl esters such as vinylacetate and vinyl propionate being preferred. More specific examplesinclude methyl methacrylate, isopropenyl acetate and butyl and isobutylacrylate.

Our preferred copolymers contain from 40 to 60 mole % of a C₁₂ -C₁₄average dialkyl fumarate and 60 to 40 mole % of vinyl acetate.

Where ester polymers or copolymers are used they may conveniently beprepared by polymerising the ester monomers in a solution of ahydrocarbon solvent such as heptane, benzene, cyclohexane, or white oil,at a temperature generally in the range of from 20° C. to 150° C. andusually promoted with a peroxide or azo type catalyst, such as benzoylperoxide or azodi-isobutyronitrile, under a blanket of an inert gas suchas nitrogen or carbon dioxide, in order to exclude oxygen.

The additives of the present invention are particularly effective whenused in combination with other additives known for improving the coldflow properties of distillate fuels generally, although they may be usedon their own to impart a combination of improvements to the cold flowbehaviour of the fuel.

The additives of the present invention are particularly effective whenused with the polyoxyalkylene esters, ethers, ester/ethers and mixturesthereof, particularly those containing at least one, preferably at leasttwo C₁₀ to C₃₀ linear saturated alkyl groups and a polyoxyalkyleneglycol group of molecular weight 100 to 5,000 preferably 200 to 5,000,the alkyl group in said polyoxyalkylene glycol containing from 1 to 4carbon atoms. These materials form the subject of European PatentPublication No. 0061895 A2.

The preferred esters, ethers or ester/ethers useful in the presentinvention may be structurally depicted by the formula:

    R--O--(A)--O--R.sup.1

where R and R¹ are the same or different and may be ##STR3## the alkylgroup being linear and saturated and containing 10 to 30 carbon atoms,and A represents the polyoxyalkylene segment of the glycol in which thealkylene group has 1 to 4 carbon atoms, such as a polyoxymethylene,polyoxyethylene or polyoxytrimethylene moiety which is substantiallylinear; some degree of branching with lower alkyl side chains (such asin polyoxypropylene glycol) may be tolerated but it is preferred theglycol should be substantially linear.

Suitable glycols generally are the substantially linear polyethyleneglycols (PEG) and polypropylene glycols (PPG) having a molecular weightof about 100 to 5,000 preferably about 200 to 2,000. Esters arepreferred and fatty acids containing from 10-30 carbon atoms are usefulfor reacting with the glycols to form the ester additives and it ispreferred to use a C₁₈ -C₂₄ fatty acid, especially behenic acids. Theesters may also be prepared by esterifying polyethoxylated fatty acidsor polyethoxylated alcohols.

Polyoxyalkylene diesters, diethers, ether/esters and mixtures thereofare suitable as additives with diesters preferred for use in narrowboiling distillates. While minor amounts of monoethers and monoestersmay also be present and are often formed in the manufacturing process.It is important for additive performance that a major amount of thedialkyl compound is present. In particular stearic or behenic diestersof polyethylene glycol, polypropylene glycol orpolyethylene/polypropylene glycol mixtures are preferred.

The additives of this invention may also be used with the ethyleneunsaturated ester copolymer flow improvers. The unsaturated monomerswhich may be copolymerized with ethylene, include unsaturated mono anddiesters of the general formula: ##STR4## wherein R₆ is hydrogen ormethyl; R₅ is a --OOCR₈ group wherein R₈ is hydrogen or a C₁ to C₂₈,more usually C₁ to C₁₇, and preferably a C₁ to C₈, straight or branchedchain alkyl group; or R₅ is a --COOR₈ group wherein R₈ is as previouslydescribed but is not hydrogen and R₇ is hydrogen or --COOR₈ aspreviously defined. The monomer, when R₅ and R₇ are hydrogen and R₆ is--OOCR₈, includes vinyl alcohol esters of C₁ to C₂₉, more usually C₁ toC₁₈, monocarboxylic acid, and preferably C₂ to C₅ monocarboxylic acid.Examples of vinyl esters which may be copolymerised with ethyleneinclude vinyl acetate, vinyl propionate and vinyl butyrate orisobutyrate, vinyl acetate being preferred. We prefer that thecopolymers contain from 20 to 40 wt.%. of the vinyl ester morepreferably from 25 to 35 wt.% vinyl ester. They may also be mixtures oftwo copolymers such as those described in U.S. Pat. No. 3,961,916.

It is preferred that these copolymers have a number average molecularweight as measured by vapor phase osmometry of 1000 to 6000, preferably1000 to 3000.

The additives of the present invention may also be used in distillatefuels in combination with polar compounds, either ionic or nonionic,which have the capability in fuels of acting as wax crystal growthinhibitors. Polar nitrogen containing compounds have been found to beespecially effective when used in combination with the glycol esters,ethers or ester/ethers and such three component mixtures are within thescope of the present invention. These polar compounds are generallyamine salts and/or amides formed by reaction of at least one molarproportion of hydrocarbyl substituted amines with a molar proportion ofhydrocarbyl acid having 1 to 4 carboxylic acid groups or theiranhydrides; ester/amides may also be used contain 30 to 300 preferably50 to 150 total carbon atoms. These nitrogen compounds are described inU.S. Pat. No. 4,211,534. Suitable amines are usually long chain C₁₂ -C₄₀primary, secondary, tertiary or quarternary amines or mixtures thereofbut shorter chain amines may be used provided the resulting nitrogencompound is oil soluble and therefore normally containing about 30 to300 total carbon atoms. The nitrogen compound preferably contains atleast one straight chain C₈ -C₄₀ preferably C₁₄ to C₂₄ alkyl segment.

Suitable amines include primary, secondary, tertiary or quaternary, butpreferably are secondary. Tertiary and quarternary amines can only formamine salts. Examples of amines include tetradecyl amine, cocoamine,hydrogenated tallow amine and the like. Examples of secondary aminesinclude dioctadecyl amine, methyl-behenyl amine and the like. Aminemixtures are also suitable and many amines derived from naturalmaterials are mixtures. The preferred amine is a secondary hydrogenatedtallow amine of the formula HNR₁ R₂ wherein R₁ and R₂ are alkyl groupsderived from hydrogenated tallow fat composed of approximately 4% C₁₄,31% C₁₆, 59% C₁₈.

Examples of suitable carboxylic acids for preparing these nitrogencompounds (and their anhydrides) include cyclo-hexane 1,2 dicarboxylicacid, cyclohexene dicarboxylic acid, cyclopentane 1,2 dicarboxylic acid,naphthalene dicarboxylic acid and the like. Generally these acids willhave about 5-13 carbon atoms in the cyclic moiety. Preferred acidsuseful in the present invention are benzene dicarboxylic acids such asortho-phthalic acid, para-phthalic acid, and meta-phthalic acid.Ortho-phthalic acid or its anhydride is particularly preferred. Theparticularly preferred compound is the amide-amine salt formed byreacting 1 molar portion of phthalic anhydride with 2 molar portions ofdi-hydrogenated tallow amine. Another preferred compound is the diamideformed by dehydrating this amide-amine salt.

The relative proportions of additives used in the mixtures are from 0.5to 20 parts by weight of the polymer of the invention containing then-alkyl groups containing an average of 12 to 14 carbon atoms to 1 partof the other additives such as the polyoxyalkylene esters, ether orester/ether, more preferably from 1.5 to 9 parts by weight of thepolymer of the invention.

The additive systems of the present invention may conveniently besupplied as concentrates for incorporation into the bulk distillatefuel. These concentrates may also contain other additives as required.These concentrates preferably contain from 3 to 75 wt.%, more preferably3 to 60 wt.%, most preferably 10 to 50 wt.% of the additives preferablyin solution in oil. Such concentrates are also within the scope of thepresent invention.

The present invention is illustrated by the following Examples in whichthe effectiveness of the additives of the present invention as pourpoint depressants and filterability improvers were compared with othersimilar additives in the following tests.

By one method, the response of the oil to the additives was measured bythe Cold Filter Plugging Point Test (CFPP) which is carried out by theprocedure described in detail in "Journal of the Institute ofPetroleum", Volume 52, Number 510, June 1966, pp. 173-185. This test isdesigned to correlate with the cold flow of a middle distillate inautomotive diesels.

In brief, a 40 ml sample of the oil to be tested is cooled in a bathwhich is maintained at about -34° C. to give non-linear cooling at about1° C./min. Periodically (at each one degree Centrigrade drop intemperature starting from at least 2° C. above the cloud point) thecooled oil is tested for its ability to flow through a fine screen in aprescribed time period using a test device which is a pipette to whoselower end is attached in inverted funnel which is positioned below thesurface of the oil to be tested. Stretched across the mouth of thefunnel is a 350 mesh screen having an area defined by a 12 millimeterdiameter. The periodic tests are each initiated by applying a vacuum tothe upper end of the pipette whereby oil is drawn through the screen upinto the pipette to a mark indicating 20 ml of oil. After eachsuccessful passage the oil is returned immediately to the CFPP tube. Thetest is repeated with each one degree drop in temperature until the oilfails to fill the pipette within 60 seconds. This temperature isreported as the CFPP temperature. The difference between the CFPP of anadditive free fuel and of the same fuel containing additive is reportedas the CFPP depression by the additive. A more effective flow improvergives a greater CFPP depression at the same concentration of additive.

Another determination of flow improver effectiveness is made underconditions of the flow improver distillate operability test (DOT test)which is a slow cooling test designed to correlate with the pumping of astored heating oil. In this test the cold flow properties of thedescribed fuels containing the additives were determined by the DOT testas follows. 300 ml of fuel are cooled linearly at 1° C./hour to the testtemperature and the temperature then held constant. After 2 hours at thetest temperature, approximately 20 ml of the surface layer is removed asthe abnormally large wax crystals which tend to form on the oil/airinterface during cooling. Wax which has settled in the bottle isdispersed by gentle stirring, then a CFPP filter assembly is inserted.The tap is opened to apply a vacuum of 500 mm of mercury, and closedwhen 200 ml of fuel have passed through 1 the filter into the graduatedreceiver. A PASS is recorded if the 200 ml are collected within tenseconds through a given mesh size or a FAIL if the flow rate is too slowindicating that the filter has become blocked.

CFPP filter assemblies with filter screens of 20, 30, 40, 60, 80, 100,120, 150, 200, 250 and 350 mesh number are used to determine the finestmesh (largest mesh number) the fuel will pass. The larger the meshnumber that a wax containing fuel will pass, the smaller are the waxcrystals and the greater the effectiveness of the additive flowimprover. It should be noted that no two fuels will give exactly thesame test results at the same treatment level for the same flow improveradditive.

The Pour Point was determined by two methods, either the ASTM D 97 or avisual method in which 100 ml samples of fuel in a 150 ml narrow neckedbottle containing the additive under test, are cooled at 1° C./hour from5° C. above the wax appearance temperature. The fuel samples wereexamined at 3° C. intervals for their ability to pour when tilted orinverted. A fluid sample (designated F) would move readily on tilting, asemi-fluid (designated semi-F) sample may need to be almost inverted,while a solid sample (designated S) can be inverted with no movement ofthe sample.

The fuels used in these Examples were:

    ______________________________________                                                     ASTM-D-86 Distillation, ® C.                                      Wax           Initial             Final                                       Appearance    Boiling             Boiling                                Fuel Point         Point   20%    90%  Point                                  ______________________________________                                        A    -5            202     270    328  343                                    B    -2            202     254    340  365                                    C    -2.5          274     286    330  348                                    D    -4            155     215    335  358                                    E    -1.5          196     236    344  365                                    ______________________________________                                    

The Additives used were as follows:

Additive 1: A polyethylene glycol of 400 average molecular weightesterified with 2 moles of behenic acid.

Additive 2: A copolymer of a mixed C₁₂ /C₁₄ alkyl fumarate obtained byreaction of 50:50 weight mixture of normal C₁₂ and C₁₄ alcohols withfumaric acid and vinyl acetate prepared by solution copolymerisation ofa 1 to 1 mole ratio mixture at 60° C. using azo diisobutyronitrile ascatalyst.

The results in the CFPP and Pour Point tests were as follows:

    ______________________________________                                                                              ASTM D 97                                             Amount          CFPP    Pour                                    Fuel Additive ppm      CFPP   Depression                                                                            Point                                   ______________________________________                                        A    None              -5° C.   -9° C.                               1        500      -8° C.                                                                        3° C.                                                                           -6° C.                               2        500      -3° C.                                                                        -2° C.                                                                         -15° C.                               2:1      300:200  -9° C.                                                                        4° C.                                                                          -18° C.                               2:1      600:400  -11° C.                                                                       6° C.                                                                          -18° C.                          B    None              -4° C.   -6° C.                               1        120                      -6° C.                               1        300      -8° C.                                                                        4° C.                                         2        180                     -15° C.                               2        300      -2° C.                                                                        -2° C.                                        2:1      180/120  -11° C.                                                                       7       -18° C.                               2:1      300/200  -13° C.                                                                       9       -21° C.                          C    None              -4° C.   -6° C.                               1        500      -8° C.                                                                        4        -3° C.                               1        1000     -7° C.                                                                        3                                                    2        1000     -2° C.                                                                        -2                                                   2:1      300/200  -6° C.                                                                        2       -12° C.                               2:1      600/400  -10° C.                                                                       6       -15° C.                          ______________________________________                                    

The additives of the invention were compared in the DOT test withAdditive 3 which was an oil solution containing 63 wt.% of a combinationof polymers comprising 13 parts by weight of an ethylene/vinyl acetatecopolymer of number average molecular weight 2500 and vinyl acetatecontent of 36 wt.% and 1 part by weight of a copolymer of ethylene andvinyl acetate of number average molecular weight 3500 and a vinylacetate content of about 13 wt. %.

    ______________________________________                                        DOT Test                                                                      ppm of additive to pass DOT (120 mesh) at -10° C.                                           Mixture of 3 Parts                                       Fuel       Additive 3                                                                              of 1 and 2 Parts of 2                                    ______________________________________                                        A          >3,000    700                                                      B          800       250                                                      C          1,500     700                                                      D          1,250     500                                                      E          >1,500    300                                                      ______________________________________                                    

Various fumarate/vinyl acetate copolymers were tested in admixture (3parts) with Additive 1 (2 parts) to determine the effect of the chainlength in the fumarate with the following results.

    ______________________________________                                             Alcohols           Pour Point                                                 used to  Average   Test     CFPP Depression                                   make     C Number  Appearance                                                                             500    1,000                                 Fuel fumarate in fumarate                                                                             at -10° C.                                                                      ppm (ai)                                                                             ppm (ai)                              ______________________________________                                        A    C-8       8        S        2      3                                          C-9       9        --       2      --                                         C-10     10        S        3      3                                          C-10/C-12                                                                              11        S        3      4                                          C-11     11        --       3      3                                          C-12     12        S        3      4                                          C-12/C-14                                                                              13        F        5      7                                          C-14     14        F        -2     -2                                    ______________________________________                                                                    Pour Point                                                                             CFPP                                                       Average   Test     Depression                                    Alcohols used                                                                              C Number  Appearance                                                                             300                                      Fuel to make fumarate                                                                           in fumarate                                                                             at -10° C.                                                                      ppm                                      ______________________________________                                        B    C-8           8        S        3                                             C-9           9        --       5                                             C-10         10        S        4                                             C-10/C-12    11        S        5                                             C-11         11        --       5                                             C-12         12        S        3                                             C-12/C-14    13        F        7                                             C-14         14        F        0                                                                             1,000                                                                         ppm                                      C    C-10         10                 3                                             C-10/C-12    11                 3                                             C-11         11                 3                                             C-12         12                 3                                             C-12/C-14    13                 6                                             C-14         14                 0                                             C-18         18                 3                                        ______________________________________                                    

Various fumarate/vinyl acetate copolymers obtained from differentalcohols but averaging 12 to 13.5 carbon atoms in the alkyl groups weretested in the same mixture as in the previous example in the CFPP andVisual pour point tests with the following results.

    __________________________________________________________________________                             Fuel A       Fuel B       Fuel C                                         Alcohol                                                                            CFPP Depression Pour                                                                       CFPP  Pour   CFPP  Pour                 Fumarate Alcohols   Average                                                                             Point       Depression                                                                          Point  Depression                                                                          Point                (All n-alcohols except oxo-C-13)                                                                  C-   500                                                                              1000                                                                             Appearance                                                                           300                                                                              500                                                                              Appearance                                                                           1000  Appearance           Ratio's by weight   number                                                                             ppm                                                                              ppm                                                                              at -10° C.                                                                    ppm                                                                              ppm                                                                              at -10° C.                                                                    ppm   at -10°       __________________________________________________________________________                                                             C.                     C-12/C-14 = 1/1   13.0 5  7  F      7  9  F      6     F                      C-12/C-14 = 3/1   12.5 2  4  Semi-F 6  6  Semi-F 3                            C-12/C-14 = 1/3   13.5 0  1  F      2  5  F      0     --                     C-10/C-16 = 1/1   13.0 -2 -1 F      2  1  F      1     --                     C-13 oxo (from tetrapropylene)                                                                  13.0 3  -- S      5  5  S      3     --                     C-12/C-14/C-16 = 2/1/1                                                                          13.5 1  -- --     1  -- --     0     --                     C-12/C-14/C-16 = 8/3/1                                                                          12.7 4  7  F      7  9  F      7     F                      C-8/C-10/C-12/C-14/C-16/C-18 =                                                                  12.2 4  6  F      4  7  F      2     F                      9/11/36/30/10/4                                                               C-8/C-10/C-12/C-14/C-16/C-18 =                                                                  13.0 0  1  --     2  2  --     1                            3/8/33/37/12/8                                                              10.                                                                             C-12/C-14/C-16/C-18 = 45/38/12/5                                                                13.4 0  0  --     2  2  --     1     --                     C-8 to C-18 = 13/10/41/15/9/13                                                                  12.5 2  3  --     4  6  --     1     --                   __________________________________________________________________________

The fuels B and C were used in the following Examples together with

    ______________________________________                                        Fuel    ASTM D-86 Distillation ° C.                                    ______________________________________                                        F      IBP       20%     50%     90%   FBP                                           182       254     285     324   343                                    ______________________________________                                    

The results are CFPP and visual Pour Point results shown for variousadditives in the following table. Where the additive has no pourdepressing effect the CFPP value is not measured because without pourdepression the fuel cannot be used.

    __________________________________________________________________________    Fuel B                                                                        CFPP Depression                                                                                            400 ppm                                          Additive              Fumarate                                                                             fumarate/vinyl acetate                           Alcohol content of                                                                        400 ppm   vinyl acetate                                                                        100 ppm Additive 1                               Fumarate    100 ppm   Additive 1                                                                           100 ppm Additive 3                               __________________________________________________________________________    C.sub.4                      2                                                C.sub.6                      2                                                C.sub.8                      2                                                C.sub.9     No pour depression*                                                                            2                                                C.sub.10                     2                                                C.sub.11                     2                                                C.sub.12                     2                                                C.sub.13    7° C.     8                                                C.sub.14    0                2                                                C.sub.16    Raised by 2° C.                                                                         Raised by 2° C.                           C.sub.18    No pour depression*                                               C.sub.22                                                                      Mixed C.sub.12 /C.sub.14                                                      3:1         No effect        2                                                1:1         8° C.     9                                                1:3         4° C.     5                                                C.sub.18 /C.sub.16                                                                        Raised by 1° C.                                                                         Raised by 1° C.                           1:1                                                                           C.sub.10 /C.sub.12                                                                        No effect        2                                                __________________________________________________________________________     *No pour depression observed at -10°  C. after the 1°           C./hour cool.                                                            

    __________________________________________________________________________    CFPP Depression                                                               Additive    Fuel C    Fuel F    800 ppm F/VA                                  Alcohol content of                                                                        800 ppm F/VA                                                                            800 ppm F/VA                                                                            200 ppm 1                                     Fumarate    200 ppm Additive 1                                                                      200 ppm Additive                                                                        100 ppm 3                                     __________________________________________________________________________    C.sub.4                                                                       C.sub.6                                                                       C.sub.8                                                                       C.sub.9     No pour depression*                                               C.sub.10                                                                      C.sub.11                                                                      C.sub.12                                                                      C.sub.13    3         9         4                                             C.sub.14    0         1         1                                             C.sub.16    0         2         1                                              C.sub.18                                                                                 No pour depression* --                                            C.sub.22                                                                      Mixed C.sub.12 /C.sub.14                                                      3:1         No pour depression* 1                                             1:1         4         10        8                                             1:3         1         4         4                                             C.sub.18 /C.sub.16                                                            1:1         0         0         1                                             C.sub.10 /C.sub.12                                                            1:1         No pour depression* 2                                             __________________________________________________________________________     *No pour depression observed at -10° C. after the 1 hour cool     

The Additives were also tested in combination with Additive 4 the halfamide formed by reacting two moles of hydrogenated tallow amine withphthalic anhydride and the CFPP depressions in Fuel B were as follows

    ______________________________________                                        Additive          CFPP Depressions                                            ______________________________________                                        Additive 4 (250 ppm)                                                                            6                                                           Additive 3 (100 ppm)                                                          C.sub.12 /C.sub.14 F/VA (250 ppm)                                             Additive 4 (300 ppm)                                                          Additive 1 (100 ppm)                                                                            6                                                           C.sub.12E /C.sub.14 F/VA (100 ppm)                                            Additive 4 (250 ppm)                                                                            0                                                           C.sub.12 /C.sub.14 F/VA (250 ppm)                                             ______________________________________                                    

We claim:
 1. A distillate petroleum fuel oil boiling in the range of120° to 500° C. having a cold flow property improving amount of acopolymer present therein, said copolymer consisting essentially ofpolyvinylester containing at least 25 weight percent of repeatingmonomer units of monoethylenically unsaturated C₄ to C₈ mono- ordicarboxylic acids esterified with at least 2 different n-alkyl groupswherein (1) said n-alkyl groups have an average number of carbon atomsof from 12 to 14; (2) no more than 10 wt. % of said esterified monomerunits contain n-alkyl groups having more than 14 carbon atoms; and (3)no more than 20 wt. % of said esterified monomer units contain n-alkylgroups having fewer than 12 carbon atoms.
 2. The distillate petroleumfuel oil of claim 1 wherein said fuel oil is sharply fractionated having(a) its 20 to 90% distillation points differ by less than 100° C., (b)its 90% distillation to final boiling points differ by 10° to 25° C. and(c) a final boiling point in the range of 240° to 380° C.
 3. Thedistillate petroleum fuel oil of claim 1 wherein said polyvinylestercontains from about 10 to 50 wt. % of comonomer selected from the groupconsisting of alkyl acrylate, methacrylate and mixtures thereof.
 4. Thedistillate petroleum fuel oil of claim 1 wherein said repeatingesterified monomer units of the polyvinylester comprise dialkyl fumaratemonomer units.
 5. The distillate petroleum fuel oil of claim 4 whereinsaid polyvinylester contains from 60 to 40 mole % of vinyl acetatemonomer units and 40 to 60 mole % dialkyl fumarate monomer units.
 6. Thedistillate petroleum fuel oil of claim 5 wherein all the n-alkyl groupsof said dialkyl fumarate comonomer units contain from 12 to 14 carbonatoms.
 7. The distillate petroleum fuel oil of claim 4 wherein then-alkyl groups of said dialkyl fumarate monomer units are about a 50/50molar mixture of C₁₂ and C₁₄ alkyl groups.
 8. The distillate petroleumfuel oil of claim 1 which contains from about 0.001 to about 0.5 wt. %of said polyvinylester.
 9. The distillate petroleum fuel oil of claim 1which further contains a copolymer of ethylene and vinyl acetate.
 10. Anadditive concentrate comprising an oil solution containing 3 to 75 wt. %of a copolymer consisting essentially of polyvinylester containing atleast 25 wt. % of repeating monomer units of mono-ethylenicallyunsaturated C₄ to C₈ mono- or dicarboxylic acids esterified with atleast two different n-alkyl groups wherein (1) said n-alkyl groups havean average number of carbon atoms of from 12 to 14; (2) no more than 10wt. % of said esterified monomer units contain n-alkyl groups havingmore than 14 carbon atoms; and (3) no more than 20 wt. % of saidesterified monomer units contain n-alkyl groups having fewer than 12carbon atoms.
 11. The additive concentrate of claim 10 wherein saidpolyvinylester contains from about 10 to 50 wt. % of comonomer selectedfrom the group consisting of alkyl acrylate, methacrylate and mixturesthereof.
 12. The additive concentrate of claim 11 wherein said repeatingesterified monomer units of the polyvinylester comprise dialkyl fumaratemonomer units.
 13. The additive concentrate of claim 12 wherein saidpolyvinylester contains from 60 to 40 mole % of vinyl acetate monomerunits and 40 to 60 mole % dialkyl fumarate monomer units.
 14. Theadditive concentrate of claim 13 wherein all the n-alkyl groups of saiddialkyl fumarate comonomer units contain from 12 to 14 carbon atoms. 15.The additive concentrate of claim 12 wherein the n-alkyl groups of saiddialkyl fumarate monomer units are about a 50/50 molar mixture of C₁₂and C₁₄ alkyl groups.